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Si PE 002-C 550 Flow 40 60 108.9726 2.5206
Al PE 002-C 550 Flow 40 60 144.8606 2.5584
Fe PX9 150 Scint. 30 40 57.4932 0.9596
Mn PX9 150 Scint. 40 80 62.9406 0.9760
Mg PX1 150 Flow 40 60 23.1016 2.3114
Ca PX9 150 Flow 40 70 113.1196 1.0718
Na PX1 550 Flow 40 70 27.9086 2.3812
K PX9 150 Flow 50 40 136.6522 2.0056
Ti PX9 150 Flow 40 70 86.1484 0.9296
F PX1 550 Flow 30 70 43.6202 2.1876
P Ge 111-C 550 Flow 40 70 141.0412 1.9026
a
The other conditions are same for all the elements: anode, rhodium; type, Goniometer; line, K; tube lter, none; measuring
time, 20 s.
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158
Chemical analysis of phosphate rock 157
Table 4. Chemical analyses of S
1
, S
2
, S
3
, S
4a
and S
4
Specimen Chemical analyses P
2
O
5
(%) CaO (%) MgO (%) Fe
2
O
3
(%) Al
2
O
3
(%) SiO
2
(%) F (%)
S
1
XRF method 33.29 48.08 0.32 1.09 1.29 5.59 3.78
Other methods
a
33.14 48.57 0.40 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 2.55 IR 4.87 2.60
NIST analysis 33.34 0.06 48.02 0.17 0.32 0.01 1.08 0.03 1.30 0.04 5.50 0.02 3.82 0.02
S
2
XRF method 25.66 52.98 0.34 0.26 0.33 7.35 3.48
Other methods
a
25.25 49.59 0.49 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 0.49 IR 3.23 2.90
S
3
XRF method 17.36 57.72 0.37 0.32 0.46 5.84 2.93
Other methods
a
19.52 51.69 0.49 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 0.49 IR 3.23 2.90
S
4a
XRF method 23.37 51.17 1.73 0.29 0.39 3.48 3.50
S
4
XRF method 26.63 50.23 1.26 0.59 0.81 4.49 3.61
Calculated
b
26.66 50.13 1.26 0.55 0.69 4.15 3.61
a
P
2
O
5
content was determined by spectrophotometry, CaO, MgO, R
2
O
3
and SiO
2
contents by gravimetry and uorine by the
volumetric method.
b
The contents of S
4
were calculated by component balance using the mass fractions of the specimens.
gravimetric method became inaccurate and gave incorrect
results for the tailings (phosphate rejected in the mines). This
is dolomitic phosphate with a high CaO content of about
57.72% and a high CaO/P
2
O
5
ratio, i.e. 3.32, as found by
XRF, but the gravimetric method gave a 51.69% CaO content
and the CaO/P
2
O
5
ratio of 2.65.
The specimen S
4
was prepared by taking 2 g of a
specimen (S
4a
) analysed by XRF spectrometry and blending
it with 1 g of SRM 120c so that the mass fractions of the
specimens were 0.67 and 0.33, respectively. The specimen
obtained was ground to 300 mesh particle size and
analysed by XRF spectrometry; the chemical analyses of
the resultant specimen (S
4
) are given in Table 4. From
the component material balance and comparison with the
analytical results for the specimen obtained (means between
the experimental and the theoretical results), the same values
for the F and MgO contents were found for both the
calculated and analytical results. The absolute errors for
P
2
O
5
, SiO
2
, Al
2
O
3
, Fe
2
O
3
and CaO were 0.03, 0.34, 0.12, 0.04
and 0.1 and the relative errors were 0.001, 0.08, 0.15, 0.07 and
0.002, respectively.
From the above results, it is clear that the XRF spectro-
metric method gave more accurate results and can be used
for larger range of concentrations and for all major elements
in phosphate rock with a wide range of standards. In the XRF
method the standards used should have a similar chemical
composition to the specimen being analysed, e.g. phosphate
rock with MgO contents >3.00% can not be analysed using
the given standards in this work and it may give wrong
results when dolomite pebbles with higher MgO contents
are analysed. Different standards may be required for spec-
imens obtained from other mines. Table 5 shows the range
of the analyte elements and the range of variations, and it is
evident that XRF shows high accuracy for the major, minor
and trace elements in phosphate rock.
In the volumetric method, several chemical processes
have to be carried out for preparation of chemicals,
calcination, digestion, boiling, distillation, agitation neutral-
ization and titration. The volumetric method is not precise
for the determination of uorine content. The gravimetric
method becomes inaccurate with low-grade phosphate rock
Table 5. Accuracy of XRF for the determined and
undetermined elements
Analyte Range of content (%) Range of variation ()
SiO
2
4.111.2 0.20.4
Al
2
O
3
0.21.8 0.10.04
Fe
2
O
3
0.21.1 0.030.06
MnO 0.010.03 0.0010.002
MgO 0.31.6 0.010.02
CaO 43.656.3 0.080.4
Na
2
O 0.80.5 0.0010.02
K
2
O 0.10.5 0.0040.02
TiO
2
0.10.02 0.0040.006
F 2.24.0 0.020.1
P
2
O
5
15.037.0 0.040.1
(i.e. tailings rejected in the mines) so it cannot be used for
dolomitic phosphate where the P
2
O
5
content is low and that
of CaO is high. Even with high-grade rock (high P
2
O
5
con-
tents) it gives inaccurate results for SiO
2
. The gravimetric
method cannot yield results for Al
2
O
3
and Fe
2
O
3
directly.
However, it gives iron oxide and aluminium oxide together.
For other major components, such as P
2
O
5
, MgO and CaO, it
can be used to determine the concentrations of unknown ele-
ments. The spectrophotometric methodcanbe utilizedfor the
determination of P
2
O
5
only for lowand high concentrations
9
and is unsuitable for intermediate concentrations.
CONCLUSIONS
XRF spectrometry is a rapid, accurate and precise method
for the elemental analysis of phosphate rock specimens and
requires simple and minimal preparation at low cost. It
has the advantage of giving separate concentrations of each
element not related to other contents. XRF spectrometry is
a non-invasive method, which means that the specimens
analysed are not destroyed or changed by exposure to x-rays
andthey canbe savedfor further use as a reference or inother
types of testing. XRF covers a wide range of concentration
using a relatively inexpensive computer for calculations but
it requires a large number of well-analysed samples for
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158
158 M. J. Sa et al.
the initial determination of the coefcients and needs an
expert with a good knowledge of software to operate the
spectrometer.
Commercial companies require XRF spectrometry in
routine analyses instead of the out-of-date methods because
the daily checking of multiple specimens in a short time can
save chemicals, time and labour and can give precise results.
REFERENCES
1. National Institute of Standards and Technology. Certicates of
Analysis of Standard Reference Materials 694 Western Phosphate
Rock and 120c Florida Phosphate Rock. SRM
Standard
Reference Materials Program. NIST: Gaithersburg, MD; 2003;
www.nist.gov/srm.
2. Association of Florida Phosphate Chemists. AFPC Analytical
Methods, 6th edn, vol. 9. AFPC Publications: Bartow, FL: 1980;
37.
3. Furman NH. Standard Methods of Chemical Analysis: the Elements,
6th edn, vol. 1. Van Nostrand: New York, 1962.
4. Govil PK. J. Geol. Soc. India 1985; 26: 38.
5. Brouwer P. Theory of XRF: Getting Acquainted with Principles, 1st
edn. PANanalytical: Almelo, 2003.
6. Wang X, Li G, Zhang Q, Wang Y. Geostand. Geoanal. Res. 2004; 28:
81.
7. Figueiredo MO, da Silva TP, Veiga JP, Chevallier P. J. Phys. IV
2003; 104: 399.
8. Frayssinet P, Braye F, Weber G. J. Scanning Microsc. 1997; 19:
253.
9. European Fertilizer Manufacturers Association. Production of NPK
Fertilizers by the Mixed Acid Route. Booklet No. 8. European
Fertilizer Manufacturers: Brussels, 2000; 1.
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158